Chlorination of dihydrothionaphthene sulfone



Patented June 29, 1954 CHLORINATION F DIHYDROTHIONAPH- THENE SULFONEJohnnE; Mahan, Bartlesville, 0kla., and Alvin C.

Rothlisbcrger, Borger, Tex., assignors to Phillips: Petroleum Company, acorporation of Delaware No Drawing. Application August 30, 1951,

7 Serial No. 244,470

4-Claims. 1

This invention relates to halogenated polycyclic sulfones and to amethod'for their preparation. In one of its more specific aspects thisinvention relates to novel halogenated-derivatives of a3a,7a-dihydrothionaphthene sulfone and to a method for the preparationthereof;

Heretofore halogenated derivatives of a 3a,- 7a-dihydrothionaphthenesulfone have been unknown. Accordingly it istan object of this inventionto prepare these materials andto provide a method fort theirpreparation.v These and other objects of the invention will'becomeapparent in the light of the accompanying disclosure.

It has now been found that halogenated derivatives of a3a,7a-dihydrothionaphthene sulfone are prepared by reacting a3a,7a-dihydrothionaphthene sulfone with a halogen selected from thegroup consisting of chlorine and bromine. Throughout this specificationand in accordance with our invention by a 3a,7a-dihydrothionaphthenesulfone is meant not only the compound 3a,7a-dihydrothionaphthenesulfone but also its various substituted derivatives, as may berepresented by the following structural formula p o s wherein R is ahydrogen atom or an alkyl, aryl, alkaryl, aralkyl or cycloalkylradicals, wherein the total number of carbon radicals present in anysuch radical is not greater than 12. Preferably the total number ofcarbon atoms present in the above-indicated structural formula is notreater than 32. The substituent radicals include the variols alkylradicals such as methyl, ethyl, propyl, tert-butyl, amyl, octyl; thevarious cycloalkyl radicals such as cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl; the various aryl, alkaryl and aralkyl radicalssuch as phenyl, benzyl, tolyl, Xylyl, cumenyl, etc. as well as thehigher and lower molecular weight homologs of the above radicals. Thepreferred starting material for the preparation of halogenated3a,7a-dihydrothionaphthene sulfone derivatives accord- 2; ing to theinvention is the. compound 3a,'7adihydrothionaphthene sulfone itself,having the empirical formula CsHaOaS andas is represented by thestructural formula HO Ht en an.

The preparation ofv 3a,7a-dihydrothionaphthene sulfone. which is: usedinthe: practice of this invention is fully described in the copendingpatent application of J. E. Mahan, filed October 25, 1951, Serial No.253,200.

The reaction between a halogen such as chlorine and/or bromine toproduce halogenated 3a,?a-dihydrothionaphthene sulfone derivatives inaccordance with our invention is carried out under the followingconditions; reaction temperature, 20 to 0., preferably between 0 and 350.; reaction time, between about 0.5 and 50 hrs.; reaction pressure, notless than that required to maintain the sulfone and solvent employed inthe liquid phase at the reaction temperature. It is preferred to employa solvent, such as chloroform, carbon tetrachloride, ether, or otherinert liquid solvent for the sulfone to be halogenated. The mol ratio ofsolvent to sulfone may vary from 1 to 20 or even higher, depending uponthe solubility characteristics of the sulfone and other reactionconditions. The halogenation agent, preferably chlorine, is added to thereaction mixture as by bubbling therethrough, at such a rate that thedesired product is obtained. The sulfone starting material hereinbeforereferred to and described may also contain some isomeric2,3-dihydrothionaphthene sulfone.

The reaction taking place between the chlorine and bromine or othersuitable halogenating agent such as iodine chloride, is primarily theaddition of halogen (chlorine if chlorine is used) to the sulfoneprobably by addition to the carbon-to-carbon double bonds. It is alsopossible that some substitutive halogenation may take place. Thehalogenated product which is obtained may vary in its halogen contentand may contain, for example 2, 4 or 6 halogen atoms.

Reaction conditions such as temperature and length of reaction periodmay be varied to yield the desired degree of halogenation.

The halogenated 3a,7a-dihydrothionaphthene sulfones have been found tobe useful as fungicides and as herbicides. The materials are also usefulas intermediates in the field of pharmaceutical chemicals and the likeas well as antioxidants, lubricating oil additives and wax modifiers.The tetrachloro derivative of 3a,7a-dihydrothionaphthene sulfone asrepresented by the empirical formula CaH3C1402S has been found to befungicidal toward G. cingulata and A. olemcea and has also been found toexhibit some herbicidal activity when tested on sprouting rice.

The following example also explains and illustrates the invention.

Example The chlorination of 3a,?a-dihydrothionaphthene sulfone wascarried out as follows: 3.46 grams of the sulfone was dissolved in 30.24grams of chloroform and cooled to ice temperature. Chlorine was slowlybubbled through the solution. An excess of chlorine was added and themixture was allowed to stand overnight at ice temperature, the totalreaction time being 16 hours.

The excess chlorine and the chloroform were stripped from the reactionmixture under vacuum. The semi-solid, light yellow, chlorinated productweighed 6.91 grams. The material had a sweet, flowery odor and wassoluble in ethyl alcohol, ether and benzene. It was slightly soluble inisooctane and practically insoluble in water. The material was analyzedand was found to contain 46.7 weight per cent chlorine. The theoreticalamount of chlorine in the tetrachloro 4 derivative (empirical formulaC8H8C1402S) is 45.75 per cent by weight chlorine.

As will be evident to those skilled in the art upon reading thisdisclosure many modifications, changes and substitutions may be madewithout departing from the spirit or scope of this invention.

We claim:

1. A tetrachloro derivative of 3a,?a-dihydrothionaphthene sulfone havingthe empirical formula CaHsChOzS and prepared by reacting 3a,7adihydrothionaphthene "sulfone with chlorine.

2. A tetrahalogenated derivative of 3a,7a-dihydrothionaphthene sulfonehaving the empirical formula CsH8X402S wherein X is a halogen atomselected from the group consisting of chlorine and bromine and preparedby reacting 3a,7adihydrothionaphthene sulfone with a halogen selectedfrom the group consisting of chlorine and bromine.

3. A tetrabromo derivative of 3a,7a-dihydro thionaphthene sulfone havingthe empirical formula C8H8B1'402S and prepared by reacting3a,7adihydrothionaphthene sulfone with bromine.

4. A tetrahalogenated derivative of 3a,'7a-dihydrothionaphthene sulfonehaving the empirical formula CsHsX402S wherein X is a halogen atomselected from the group consisting of chlorine and bromine and whereinsaid tetrahalogenated derivative is prepared by reacting the said3a,?adihydrothionaphthene with a halogenating agent which yields ahalogenated derivative containing said halogen.

References Cited in the file of this patent J. A. C.

J. A. C. Bordwell 613 2.1.: J. A. C. S., 72, 1985-8 (1950).

2. A TETRAHALOGENATED DERIVATIVE OF 3A, 7A-DIHYDROTHIONAPHTHENE SULFONEHAVING THE EMPIRICAL FORMULA C8H8X402S WHEREIN X IS A HALOGEN ATOMSELECTED FROM THE GROUP CONSISTING OF CHLORINE AND BROMINE AND PREPAREDBY REACTING 3A,7ADIHYDROTHIONAPHTHENE SULFONE WITH A HALOGEN SELECTEDFROM THE GROUP CONSISTING OF CHLORINE AND BROMINE.